Express Polymer Letters Vol.17, No.

9 (2023) 900–912 êŽpŎêŔŔ

Available online at www.expresspolymlett.com
https://doi.org/10.3144/expresspolymlett.2023.67 p o ğžĥêŎ˙ğêŜŜêŎŔ
Research article

Spent coffee grounds utilization for green ultraviolet filter

and nanocomposite fabrication
Ha Ngoc Giang1* , Chanh Cong Tran2, Tuan Nguyen Anh Huynh2 , Phuong Thi Minh Doan1
˙

1Faculty of Chemical Technology, Ho Chi Minh City University of Industry and Trade, 140 Le Trong Tan Street, Tay
Thanh Ward, Tan Phu District, Ho Chi Minh City, Viet Nam
2Faculty of Chemical and Food Technology, Ho Chi Minh City University of Technology and Education, 1 Vo Van Ngan

Street, Linh Chieu Ward, Thu Duc City, Ho Chi Minh City, Viet Nam

Received 3 March 2023; accepted in revised form 12 May 2023

Abstract. Spent coffee grounds (SCGs), the main by-product in the coffee industry, were proposed as a starting material to
fabricate both ultraviolet (UV) shielding material and nanocomposite based on polyvinyl alcohol (PVA). The extract using
low SCGs concentration (0.25 wt%) contains a significant amount of UV-absorbing substances. The UV shielding film from
5 wt% PVA solution and SCGs extract (1 g SCGs/200 ml water) could shield most of the radiation in UV-B and UV-C
regions and maintain 63% transmittance at 550 nm. The SCGs after washing were ball milled and the ultrasonic liquid
processor was applied to synthesize SCGs nanoparticle. The effects of ultrasonic amplitude and hexadecyltrimethylammo-
nium bromide (CTAB) on the particle’s hydrodynamic diameter were investigated. The particle’s size of 148 nm was obtained
with 50% ultrasonic amplitude. Fourier-transformed infrared spectroscopy (FTIR) results confirmed the presence of hydroxyl
groups (–OH) on the SCGs-based nanoparticle’s surface. The tensile strength of PVA-SCGs nanocomposite was significantly
improved. However, the presence of CTAB in the nano solution could not show a better tensile result. The organic compounds
contained in the SCGs extract and even in the nano SCGs solution could enhance thermal oxidation stability for both UV
shielding films and nanocomposites.

Keywords: nanomaterials, polymer composites, reinforcements, spent coffee grounds, UV filter

1. Introduction potential source of natural antioxidant compounds.

Coffee has become one of the most popular bever- In a recent study, many products from SCGs could
ages in many countries and massive waste including be utilized by extracting in water and hydrothermal
spent coffee grounds (SCGs) has been generated by liquefaction [10]. Many substances including poly-
the industry [1, 2]. Because of their low economic phenol, polysaccharide, ketone, acid, ester etc. could
value, SCGs are often discarded as waste and it be detected. Therefore, SCGs were considered as a
might affect human health and the environment [3]. bioresource that can be utilized for many applica-
The SCGs composition is highly varied because of tions. With high nutrient content, SCGs have been
different brewing methods and types of coffee. The applied as a bio-fertilizer in agriculture [11, 12].
main SCGs’ components include carbohydrates, Properties of caffeine and other components from
lignin, lipids, and protein [4–6]. Even after brewing, coffee could be applied in sunscreens [13–15] or
many bioactive phenolic compounds were found in solar cells [16]. Polyvinyl alcohol (PVA), a water-sol-
SCGs [7–9]. These findings have made the popular uble polymer, was widely used in many applications
waste material from the coffee industry become a because of its biocompatibility [17, 18]. Therefore, a

Corresponding author, e-mail: hagn@hufi.edu.vn

*

© BME-PT

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 H. N. Giang et al. – Express Polymer Letters Vol.17, No.9 (2023) 900–912

combination of PVA and UV-absorbing substances applied to reduce the size of SCGs particles. How- R1
in instant coffee had been proposed to form an envi- ever, the rather large average size of 240 nm and R2
ronmentally friendly material that could shield lights broad size distribution was obtained. R3
in the UV region [19]. The fabricated films showed To the best of our knowledge, there is no report of R4
good transparency and thermal stability. The com- the ability to fabricate stable SCGs nanoparticles R5
ponents of caffeine, chlorogenic acid, and melanoidin under ultrasonic irradiation. Besides, the preparation R6
were assigned for the high performance of the PVA- of the SCGs particles included the washing steps to R7
based UV shielding films. remove the water-soluble substances which might be R8
On the other hand, approximately 50 wt% of the still valuable in many cases. A simple approach and R9
SCGs were cellulose and hemicellulose [5]. There- methodology to further utilize all SCGs components R10
fore, with the high demand for bio-degradable com- are still developing. In this study, green nanoparticles R11
posite, many studies attempted to recycle SCGs as a and nanocomposites based on SCGs formed with the R12
bio-filler in plastic [20–22]. In the study by Catado assistance of an ultrasonic liquid processor shall be R13
et al. [23], the properties of pectin filled with SCGs presented. Instead of instant coffee, the ability to R14
were investigated to apply as food packaging mate- reuse the extract from SCGs that were discarded dur- R15
rials. Although the hydrophobization and the reduc- ing the washing step in the previous article [36] as R16
tion of water uptake were achieved, the mechanical green UV filters shall be confirmed and discussed. R17
properties were reduced with the addition of SCGs.
SCGs also contain a significant amount of oil (more 2. Experimental section R18
than 15%) [24, 25]. The oil extracted from SCGs 2.1. Materials R19
could be utilized for bio-diesel production [26]. From PVA (hydrolysis degree: 85-90%, viscosity: 20.5– R20
another viewpoint, oil remaining in SCGs might af- 24.5 mPa·s) was purchased from Shanghai Aladdin R21
fect the mechanical properties of the composite. Bio-Chem Technology Co. Ltd (China). Hexadecyl- R22
SCGs after oil extraction could improve the mechan- trimethylammonium bromide (CTAB) (≥98%) was R23
ical and thermal properties of the formed composites the product of Sigma-Aldrich (Merck, USA). SCGs R24
[27, 28]. Leow et al. [29] also reported the enhance- were collected from a local coffee shop. The caffeine R25
ment in Young’s modulus of epoxy resin by adding standard was obtained from the Institute of Drug R26
SCGs or oil-extracted SCGs. However, the tensile Quality Control – Ho Chi Minh City (IDQC-HCMC) R27
strength was significantly decreased because of poor (Viet Nam). The chlorogenic acid standard was sup- R28
interfacial compatibility between the hydrophilic plied by Acros Organics (Thermo Scientific, United R29
SCGs-based fillers and the hydrophobic epoxy ma- Kingdom). R30
trix. Although SCGs have been utilized as green
fillers in many studies, less research reported nano- 2.2. Methods R31
material from SCGs. In the nanotechnology field, the The fabrication methods were summarized in Figure 1 R32
use of SCGs as a reducing agent to prepare silver or which includes the preparation of UV shielding films R33
gold nanoparticles has been investigated [30–32]. In and PVA-based nanocomposites. R34
another study, lipid was removed from roasted coffee
beans using n-hexane, and the components that re- Preparation of UV shielding films R35
mained in the solid residue were utilized to synthe- The collected SCGs were washed with cold distilled R36
size cellulose nanofibers (CNF) [33]. The coffee water to remove dust and impurity. The product was R37
beans based-CNF was then applied to fabricate com- dried in the oven (80 °C) for 24 h. The dried SCGs R38
posites with PVA. Although the interaction of CNF were weighed (x [g] from 0.1 to 30 g) and put into an R39
and PVA had been discussed, the mechanical prop- Erlenmeyer flask containing 200 ml of double dis- R40
erty of the composite was not reported. In other ap- tilled water. The mixture was boiled and stirred for R41
proaches, carbon dots could be synthesized from cof- 10 min. Then, the obtained mixture was filtered, and R42
fee bean shells [34] or SCGs [35]. Lee et al. [36] the solution was placed into centrifuge tubes. The cen- R43
reported particles prepared directly from SCGs with trifugation at 5000 rpm for 10 min was applied. The R44
the ability to improve the tensile strength of PVA- aqueous SCGs extract was collected and directly used R45
based composite. There was no oil-extraction step for the next step. PVA powder was weighed and added R46
needed and the popular ball mill technique was to the extract. For the UV shielding film fabrication, R47

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 H. N. Giang et al. – Express Polymer Letters Vol.17, No.9 (2023) 900–912

Figure 1. Fabrication scheme for UV shielding and nanocomposite samples.

the PVA concentration was fixed at 5 wt% which is an aqueous solution contained nanoparticles. PVA
similar to the previous report [19] for comparison. was added into the SCGs nano-solutions to form ho-
The mixture was stirred at room temperature until a mogenous mixtures with varied polymer concentra-
clear, homogeneous solution was obtained. The poly- tions (3, 5, 8, or 10 wt%). The PVA-nano SCGs so-
meric solution was poured into a Teflon petri dish. lutions were dried in a silicone mold in ambient
The solvent was gradually evaporated at 40 °C to conditions to form PVA-based nanocomposite (PNC)
form PVA-based UV shielding (PUV) films. The films. The nanocomposite samples were named
samples were marked as PUV-x, where x is the mass PNC-y, where y is the PVA concentration in the
[g] of SCGs used in 200 ml H2O in the extraction nano-solution.
step.
2.3. Characterization
Preparation of nanoparticle solution and UV-Visible spectroscopy was applied to measure the
PVA-based nanocomposite absorbance of the SCGs extract and characterize the
The remaining solid obtained after aqueous extrac- transmission of the PUV films. The spectra were ob-
tion from the above procedure was further washed tained using a double-beam spectrophotometer
with boiled distilled water until there was no change (V730, Jasco, Japan). The scanning mode was ap-
in the solution color. This step was conducted to re- plied, and the spectra were achieved in the wave-
move water-soluble substances that remained in the length region of 250 to 700 nm.
extracted SCGs. The solid after washing was again To determine the particle size, the dynamic light
dried in the oven (80 °C) for 24 h to obtain a dry pow- scattering (DLS) technique was applied using the
der. The powder was put into a cylindrical ceramic equipment of Zetasizer Pro (Malvern, United King-
ball mill (speed: 225 rpm) for 40 min. Then, the fine dom). The backscatter system (detector angle of
powder was mixed with double distilled water (con- 173°) and the measuring temperature of 25 °C were
centration: 1 wt%). The samples with CTAB were set. The sample was equilibrated for 60 s before con-
prepared in a similar method. Instead of water, the ducting the measurement. The zeta potential values
CTAB solutions (concentration: 60 or 250 mg/100 ml were determined using the same equipment with dis-
H2O) were mixed with the ground SCGs before posable folded capillary cells. Each sample was meas-
moving to the next step. ured three times and an average value was calculat-
The mixtures in a 50 ml centrifuge tube were placed ed. In addition, a transmission electron microscope
into an ultrasonic liquid processor (Net power output: (TEM) (JEM 1010, JEOL, Japan) was also applied
500 Watt, frequency: 20 kHz, vibra-Cell VC505, to directly observe the SCGs-based nanoparticles.
Sonics & Materials, Inc., USA). A standard probe Fourier transform infrared (FTIR) measurement was
equipped with a replaceable tip (diameter: 13 mm, conducted using the equipment of FTIR-8400s (Shi-
amplitude set at 100%: 126 μm) was used. The preset madzu, Japan). The samples were mixed with KBr
sonication amplitude parameter varied at 30, 50, and powder (Nacalai Tesque, Kyoto, Japan) (approxi-
70%. The sonicated mixture was filtered using a qual- mately 0.1 wt%) and put into a stainless steel mold
itative filter paper (Grade 101, Pore size: 20–25 μm, (diameter: 1.5 cm). The pressure was applied using
Hangzhou Special Paper Industry Co., Ltd., China) a manual hydraulic press to form KBr pellets. The
or a glass fiber filter (GF/A, pore size: 1.6 μm, di- FTIR transmission mode was carried out from 4000
ameter: 47 mm, Whatman, United Kingdom) to obtain to 400 cm–1 wavenumber.

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Thermogravimetric analyzer (TGA) (TGA 55, TA extract (278.8 nm) was slightly shifted to a higher
Instruments Co., USA) was performed from room wavelength region. This phenomenon might be due
temperature to 700 °C (heating rate: 10 °C·min–1). To to the interference of the other UV-absorbing sub-
confirm the thermal oxidative stability of the sam- stances (chlorogenic acid and melanoidin) in the ex-
ples, oxygen purge gas was applied (balance/sample tract [37, 38]. The UV-Visible absorbance spectrum
flow rate: 40/25 ml/min). of the SCGs extract was identical to the reported re-
Mechanical properties were evaluated using a tensile sult using instant coffee [19]. In Figure 2 results, al-
testing machine (FS3000, Testometric, United King- though the extraction was conducted with approxi-
dom). The experiment was conducted with similar mately 0.25 wt% SCGs aqueous mixture for only
conditions compared to the published research [36]. 10 min, the absorbance values of all detected peaks
The film samples were cut into rectangular shapes were higher than 1. Therefore, it could be concluded
(15×50 mm). Thickness was measured using a digi- that the extract from SCGs might contain a signifi-
tal micrometer. The tensile test was carried out with cant amount of similar organic compounds presented
a speed of 5 mm·min–1 to obtain the stress-strain in the instant coffee solution. It is worth noting that
curve. The maximum stress and elongation values in the extraction procedure is rather simple, and the
the curve were detected. process is similar to the washing step in the previous
The homogeneity of the polymer nanocomposite study [36]. It might open a new approach to utilizing
was monitored using an optical microscope (B-293, the waste product which is cheaper than the original
Optika, Italy). The microscope was equipped with instant coffee. In the next experiment, the SCGs ex-
10× and 40× objective lenses. The magnified images tract was mixed with PVA to confirm the UV-shield-
of the samples were captured by a CMOS camera ing capability of the formed films.
and exported using Optika Proview software. The transmittance values and the images of PVA
films mixed with different types of SCGs extracts
3. Results and discussion were summarized in Figure 3. The UV-shielding abil-
Figure 2 showed the UV-Visible absorbance spec- ity of the film samples might be affected by the thick-
trum of the extract obtained from 0.5 g SCGs in ness of the film sample. Therefore, the values of trans-
200 ml H2O. As can be seen, the spectrum contained mittance divided by the corresponding thicknesses
two main peaks at 278.8 and 322.8 nm. Compared to (in micrometer) were also shown in Figure 3b. How-
the pure substances (caffeine and chlorogenic acid) ever, the relative positions of the spectra obtained in
which are usually presented in coffee extract, the Figure 3b are similar to that in Figure 3a. As can be
peak at 322.8 nm might be originally from chloro- observed, pure PVA film provides the highest trans-
genic acid. However, compared to caffeine’s spec- parency. However, PVA also had the worse protec-
trum (peak is at 272.4 nm), the detected peak in the tion in the region of UV-A, B, and C (the wavelength
is less than 400 nm). When the amount of SCGs used
for aqueous solution extraction was 5, 10, 20, or
30 g/200 ml H2O, the UV region might be complete-
ly cut off after passing the PVA-based films. The
transparency in the visible region was also reduced
accordingly. On the other hand, when only 0.1 or
0.5 g SCGs was used, the transmittance values at the
visible wavelengths were improved. However, there
was part of UV light that might be allowed to pass
through the films. The sample prepared with only 1 g
SCGs provided a reasonable transmittance for the
visible lights. The transmittance measured at 550 nm
is 63% while this value is 84% for the pure PVA film.
Few wavelengths in the UV-A region remained slight-
Figure 2. UV-Visible absorption spectra (250 to 700 nm) of ly transparent. However, more damaging UV radia-
SCGs extract (0.5 g/200 ml H2O), caffeine, and tion from 290 to 350 nm could be mostly shielded.
chlorogenic acid solution (30 ppm). The investigation showed that the extracted solution

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Figure 3. a) UV-Visible spectra, b) transmittance values/film’s thicknesses spectra, and c) images of PVA film and PVA-
based films mixed with various SCGs extractions.

obtained from only 1 g SCGs/200 ml H2O (0.5 wt%) amplitude was varied, and the DLS particle size re-
could provide a similar UV-shielding effect to the sults of the obtained nanoparticle were summarized
use of 1 wt% of instant coffee reported by the other in Figure 4 and Table 1. In this investigation, although
group [19]. the conventional filter paper was applied in the filtra-
The SCGs after aqueous extraction was further uti- tion step, the average particle size of less than 300 nm
lized to synthesize nano-fillers. The washed SCGs still could be achieved. As can be seen, when the am-
were ball-milled before forming nanoparticles under plitude was increased, the smaller Z-average values
the ultrasonic force in an aqueous solution. Ultrasonic might be obtained (Table 1). In all cases, although

Figure 4. a) Plots of the correlation coefficient as a function of time and b) intensity size distribution spectra of SCGs nanopar-
ticle solutions fabricated using qualitative filter papers and various ultrasonic amplitudes.

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Table 1. DLS results of SCGs nanoparticle solutions using unchanged. In addition, the solution temperature
qualitative filter papers and various ultrasonic am- quickly increased, and it is difficult to control.
plitudes. Therefore, the amplitude of 50% was applied for the
Amplitude
30 50 70 next investigation.
[%]
Z-Average [nm] 242.6±12.5 154.3±1.0 152.3±0.9
Instead of the qualitative filter paper, the glass fiber
Polydispersity index, PI 0.532±0.071 0.333±0.028 0.291±0.002 filter with a smaller pore size was used to confirm
Peak mean (Intensity the ability to further reduce the particle size. The
386.9±91.7 171.2±25.8 208.3±18.6
distribution) [nm] DLS results were shown in Table 2. As can be seen,
the particle size was slightly improved by applying
the polydispersity index (PI) values were not large, the glass fiber filter. Figure 5 showed the TEM im-
there were other small peaks that appeared in the ages of the SCGs particles prepared without using
DLS intensity distribution which indicated two types CTAB. As can be seen, this is another evidence that
of the particle system. It is worth noting that the the nanoparticles could be successfully fabricated
SCGs components after washing might be mainly from SCGs with the assistance of ultrasonication.
carbohydrates. Cellulose, hemicellulose, and lignin Although small particles (<100 nm) could be ob-
which are varied in molecular weight in SCGs might served, many large particles and aggregations were
be the main reason for the polydispersity of the nano also detected. The TEM images were in agreement
solutions. The amplitude represents the distance of with the polydispersed distribution obtained in the
the ultrasonic tip vibrating from the equilibrium po- DLS results. Because of the ability to stabilize the
sition. Because the SCGs concentration dispersed in nanoparticle, CTAB has been widely applied in
water was fixed, the increase in amplitude was di- nanomaterials research [39–41]. Therefore, in this
rectly proportional to the ultrasonic energy used to study, the nanoparticle formed under the presence of
break down the milled SCGs into smaller particles. CTAB was investigated and the size values were also
Therefore, there was a significant difference between
Table 2. DLS results of SCGs nanoparticle solutions using
the results obtained from 30 and 50% amplitude. The
glass fiber filters and various CTAB concentrations.
size distribution was also shifted to a smaller size re-
CTAB
gion. When the amplitude was up to 70%, although [mg/100 ml]
0 60 250
the intensity signal of the smaller particle system Z-average [nm] 148.4±0.7 308.9±3.0 190.7±3.5
was slightly increased, the distribution was also Polydispersity index, PI 0.214±0.002 0.308±0.008 0.255±0.016
stretched to the larger particle area. However, the au- Peak mean (Intensity
179.1±15.9 480.8±158.7 208.3±18.6
tocorrelation curves and Z-average values were nearly distribution) [nm]

Figure 5. TEM images of SCGs-based nanoparticle sample without CTAB at a magnification of a) 10 000× and b) 30 000×.

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shown in Table 2. The larger particle size was ob- protocol is significantly smaller than the previous re-
tained with 60 mg/100 ml CTAB. By increasing to port (240 nm) [36]. Without removing the solvent,
250 mg/100 ml, although the particle size could be the nanoparticles dispersed in water were directly
reduced to 190 nm, the result still is higher than that used for the next steps of nanocomposite fabrication
of the sample formed without CTAB (148 nm). This to limit the ability of aggregation.
phenomenon might be due to the capping effect of The nanoparticles prepared using glass filter paper
CTAB on the formed nanoparticles [42]. The CTAB were added into the PVA matrix to confirm the abil-
structure contains a hydrophilic headgroup (quater- ity to improve the mechanical properties. The tensile
nary amine) and a hydrophobic tail (alkyl chain). results for the samples fabricated from the nano so-
The SCGs-based nanoparticle with the hydrophilic lution with and without CTAB (250 mg/100 ml
surface could be covered by CTAB molecules via H2O) were shown in Figure 6. Firstly, the film sam-
the charged headgroups. The second layer might be ples were fabricated using 5 and 3 wt% of PVA
formed by the interaction of hydrophobic alkyl (PNC-5 or 3 and PNC-5-CTAB or 3-CTAB) and the
chains among the CTAB molecules. As a result, the tensile results were compared. As can be seen, when
CTAB bilayer left the positive headgroups exposed the SCGs particles prepared with CTAB were mixed
to the solution. Therefore, the hydrodynamic diam- with PVA, the tendency of reducing tensile strength
eter detected by the DLS technique might be in- (TS) was obtained. The mechanical enhancement
creased. This explanation was reconfirmed by consid- could not be observed in all samples with the pres-
ering the particle surface’s charge. The zeta potential ence of CTAB. The component of SCGs might con-
was –17.7±1.6 mV while this value was positive tain fatty acids which are difficult to remove during
(25.3±0.4 mV) by adding CTAB to the solution. The the washing step with pure water. However, these
average particle size obtained by applying the current components might leak to the formed nano solution

Figure 6. Tensile result for PVA-based nanocomposites from SCGs: a) with CTAB; b) without CTAB.

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with the presence of a surface-active reagent of and decrease of elongation were obtained. To further
CTAB. These long alkyl chain components might act confirm the compatibility of PVA molecules and
as a plasticizer in the PVA matrix and reduce the me- SCGs nanoparticles, FTIR measurement was per-
chanical properties. In addition, the nanoparticles formed, and the results were summarized in Figure 9.
covered by CTAB molecules might not be compati- The nanoparticle was prepared via two steps of me-
ble with the PVA matrix. Therefore, the study was fo- chanical treatment including ball milling and ultra-
cused on the samples without using CTAB. On the sonic radiation. The FTIR spectra shown in Figure 9a
other hand, when SCGs nanoparticles prepared with- could reveal the changing of functional groups with
out CTAB were added, TS was significantly im- each step. The obtained results of SCGs were similar
proved. The highest TS value (~58 MPa) achieved to the previous publication [29]. The peaks at 2923
with 8 wt% of PVA (PNC-8) was more than two and 2853 cm–1 assigned as asymmetric and symmet-
times higher than that of the original PVA film ric C–H vibrations appeared in all SCGs samples.
(~24 MPa). The same SCGs nano solution was used The peak at 1745 cm–1 belonging to C=O bond
in all cases while the PVA concentration was de- stretching was also detected in all types of SCGs.
creased. After evaporating water to form nanocom- The C=O signal might come from various antioxi-
posite, the film samples with less PVA had a higher dant substances contained in the SCGs such as caf-
nanoparticle concentration. When the PVA concen- feine, chlorogenic acid, or fatty acids. Although the
tration was 5 wt%, the number of SCGs nanoparticles signal of this functional group became weaker in the
contained in the composite was high enough to cause nanoparticle FTIR spectrum, the existence of C=O
some aggregation (Figure 7c). This might be the main might still indicate a small amount of the bio-active
reason for the reduction of the mechanical properties. components remained. In the 4000–3200 cm–1 region,
Although the sample of PNC-3 still showed a high peaks could not be detected clearly in the SCGs after
TS value, the aggregation of nanoparticles because washing with boiled water. However, some small
of high concentration could not be ensured as can be peaks in this region belonging to O–H or N–H bond
observed in Figure 7d. In addition, the TS value could stretching appeared in the SCGs sample after the ball
not be further improved compared to the PNC-8 sam- milling process. This result indicated that the wash-
ple. A smaller nanoparticle concentration with higher ing process had removed most of the water-soluble
mechanical properties was preferred. Interestingly, substances from the SCGs’ surface. However, after
the PNC-10 sample with the smallest amount of milling, the raw SCGs were broken down into small-
nanoparticles showed an improvement in both TS er pieces and these functional groups trapped inside
and elongation at break values. might be again detectable. Interestingly, the nanopar-
The effect of SCGs nanoparticles on the stress-strain ticle showed a large peak at 3429 cm–1. In this study,
curves was shown in Figure 8. All samples showed water was used as a dispersed environment and only
the first linear increase of stress followed by yielding particles with the polar groups can be stabilized in
and plastic deformation. Compared to PVA, the elas- the medium. Therefore, SCGs-based nanoparticle sur-
tic region was significantly expanded to a higher faces might be covered by –OH groups. This might
stress region in the samples with nanoparticles addi- be one of the advantages of the current fabrication
tion (except the PNC-5 sample). These samples also method. Because of the presence of polar groups, the
performed a slight decrease of stress after yielding synthesized nanoparticle might be dispersed better
which is the typical necking in the tensile test. This in the matrix of PVA which also possesses many hy-
phenomenon is because of the formation of localized droxyl groups in the side chain. Figure 9b showed
domains in which the polymer chains were re-ori- the spectrum of PVA in which the FTIR peaks were
ented to a fibrous structure. The nanoparticle occu- also detected at similar wavenumbers compared to
pied in the spaces between the polymer chains might the previous study [43]. As can be observed, the
assist the unfolding process. Therefore, the PNC-10 PNC-8 sample’s FTIR spectrum contained the main
sample with a low nanoparticle concentration could peaks originating from its components. However, in
possess good performance in both TS and elongation the case of the nanocomposite, the large peak that
properties. However, in the PNC-8 with more appeared in the 4000–3200 region was shifted to a
nano-SCGs, the interaction of filler and polymer lower wavenumber comparing the similar peaks of
chains was dominated. As a result, the increase of TS nanoparticle and PVA. This phenomenon might be

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Figure 7. Optical microscope images of PNC at 10× and 40× objective lenses: a) PNC-10, b) PNC-8, c) PNC-5, and d) PNC-3.

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Thermal properties in the oxygen atmosphere could

reveal the capability against oxidative degradation
of the fabricated film samples. The TGA results were
summarized in Figure 10. As can be observed, the
first loss of weight occurred continuously from room
temperature until reaching 150 °C was assigned to
the evaporation of water that remained in the film
samples. The main and significant weight loss was
activated when the temperature reached 200 °C. This
large decrease in the TGA signal was because of
thermal degradation and decomposition of PVA and
organic substances in the matrix. Three types of sam-
ples (PVA, PUV, and PNC) showed similar TGA
Figure 8. Stress-strain curve of PVA-based nanocomposite transitions. To remove the interference of water des-
with SCGs. orption signals, the TGA data were normalized with
a value at 170 °C, and the results were shown in
an indicator of good compatibility between the nano- Figure 10b. As can be seen, although the difference
filler and the matrix. is small, the PUV sample still clearly showed a better

Figure 9. FTIR spectra of a) SCGs samples before and after the mechanical treatments; b) PNC-8 sample in comparison to
SCGs nanoparticle and PVA.

Figure 10. TGA results for PVA, PUV-1, and PNC-8: a) plotted from room temperature to 700 °C; b) plotted as normalized
value with weight loss at 170 °C from 160 to 265 °C.

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thermal-oxidative degradation. This result is in agree- Acknowledgements

ment with the previous report [19]. Interestingly, the The authors would like to thank MSc Le Thi Kim Anh and
weight loss signal for the PNC sample also occurred MSc Truong Thi Phuong Dung for providing laboratory as-
sistant services.
more slowly than that of the original PVA. The
nanoparticle prepared in this current study might
contain not only carbohydrate particles but also References
some amount of antioxidant remaining (caffein or [1] Murthy P. S., Madhava Naidu M.: Sustainable manage-
chlorogenic acid). Therefore, the PVA-based com- ment of coffee industry by-products and value addition
– A review. Resources, Conservation and Recycling, 66,
posite reinforced by the nanofiller from SCGs could
45–58 (2012).
possess both strong mechanical properties and resist- https://doi.org/10.1016/j.resconrec.2012.06.005
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